Method and composition for the control of fungus organisms



United States Patent METHOD AND COMPOSITION FOR THE CONTROL 2 OF FUNGUSORGANISMS Richard H. Gruenhagen, Midland, Mich., assignor to The DowChemical Company, Midland, Mich, a corporation of Delaware No Drawing.Application April 4, 1957 Serial No. 650,546

11 Claims. (Cl. 167-30) This invention is concerned with fungicides andis particular directed to compositions and methods for the control offungus organisms.

It is an object of the present invention to provide a new method for thecontrol of many common fungi. A further object of the present inventionis the provision of an improved method wherein novel compositions areemployed for fungus control. An additional object is to provide acomposition which is adapted to be applied to the aerial portions ofplants for the control of plant fungi without substantial injury to theplant foliage. Additional objects will become apparent from thefollowing specification and claims.

In accordance with the present invention, it has been discovered thatbicyclohexyl-4-amine and its inorganic acid salts are effectivefungicides and are adapted to be employed for the control of'a widerange of fungi; These amine compounds of the group consisting ofbicyclohexyl-4-amine and its inorganic acid salts are crystalline solidsreadily soluble in many organic solvents and of low solubility in water.They are adapted readily and conveniently to be employed for the controlof many fungal organisms and particularly those organisms ordinarilyfound on the aerial portions of plants. The compounds may also beapplied in dormant applications to the woody surfaces of plants or toorchard floor surfaces for the control of the overlwintering spores ofmany fungi. It is an advantage of the present invention thatcompositions containing these compounds may be applied to growingvegetation in amounts required for effective control without significantinjury to the plants. It is a further advantage that a singleapplication of the compounds will provide a residualand extended controlof fungi over a period of several months.

In carrying out the method of the present invention the undesirablefungal organisms may be controlled by contacting the organisms and/ortheir habitats with a parasiticidal amount of the unmodifiedbicyclohexyllamine or its inorganic acid salts. However, the presentinvention also embraces the employment of a liquid, powder or dustcomposition containing one or more of the toxicants. Such compositionsare adapted to be applied to the living plants without substantialinjury to the plants. In preparing toxicant compositions, the aminecompounds may be modified with one or more of a plurality of additamentsincluding organic solvents, petroleum distillates, water or other liquidcarriers, surface active dispersing agents and finely divided inertsolids. Depending upon the concentration in the composition of the amineproduct, such augmented compositions are adapted to be employed for thecontrol of the undesirable fungi or employed as concentrates andsubsequently diluted with additional inert carrier to produce theultimate treating compositions. In composi-. tions to be employed asconcentrates, the amine toxicants oftentimes are present in aconcentration from about 5 to 95 percent by weight.

The exact concentration of the bicyclohexyl-4-amine or its inorganicacid salts employed in the compositions for application to the fungusorganisms and/or their habitats may vary provided a fungicidal dosage oftoxicant is supplied either on the organism or its environment. Thisdosage of toxicant is primarily dependent upon the susceptibility of theparticular organism to the amine product. In general, good results areobtained with liquid compositions containing from about 0.001 to 2.0percent by weight of toxicant, although compositions containing as muchas 50 percent by weight may be applied to orchard floor surfaces for thecontrol of spores. With dusts, good results are obtained withcompositions containing from 0.01 to 5.0 percent or more by weight oftoxicant. Where the compositions are to be applied to living plants, itis preferred that the toxicant be present in an amount not to exceedabout 0.8 percent in liquid compositions and 1.0 percent in dusts.

In the preparation of dust compositions, the toxicant products may becompounded with any of the finely divided solids such as pyrophyllite,talc, chalk, gypsum and the like. In such operations, the finely dividedcarrier is ground or mixed with the toxicant or wet with a solution ofthe toxicant in a volatile organic solvent. Similarly, dust compositionscontaining the products may be compounded with 'various solid surfaceactive dispersing agents, such as fullers earth, bentonite, attapulgite,and other clays. Depending upon the proportions of ingredients thesedust compositions may be employed as concentrates and subsequentlydiluted with additional solid surface active dispersing agent or withpyrophyllite, chalk, talc, gypsum and the like to obtain the desiredamount of active ingredient in a composition adapted to be employed forthe control of fungi. Also, such concentrate dust compositions may bedispersed in water, with or without the aid of dispersing agents to formspray mixtures.

Further, the amine compounds or a liquid or dust concentrate compositioncontaining such compounds may be incorporated in intimate mixture withsurface-active dispersing agents such as ionic and non-ionic emulsifyingagents to form spray concentrates. Such concentrates are readilydispersible in liquid carriers to form sprays containing the toxicantsin any desired amount. The

. choice of dispersing agents and amounts thereof employed aredetermined by the ability of the agents to facilitate the dispersion ofthe concentrate in the liquid carrier to produce the desired spraycompositions.

Similarly, the toxicant products may be compounded with a suitablewater-immiscible organic liquid and a surface active dispersing agent toproduce emulsifiable concentrates which may be further diluted withwater and oil to form spray mixtures in the form of oil-in-wateremulsions. In such compositions, the carrier comprises an aqueousemulsion, i.e. a mixture of water immiscible solvent, emulsifying agentand water. Preferred dispersing agents which may be employed in thesecompositions are oil-soluble and includes the non-ionic emulsifiers suchas the condensation products of alkylene oxides with the inorganicacids, polyoxyethylene derivatives of sorbitan esters, complex etheralcohols and the like. However, oil-soluble ionic emulsifying agentssuch as mahogany soaps may also be used. Suitable organic liquids whichmay be employed in the composition include petroleum oils anddistillates, toluene, liquid halohydrocarbon and synthetic organic oils.The surface active dispersing agents are usually employed in liquidcompositions in the amount of from 1 to 20 percent by weight of the combincd weight of the dispersing agent and activecompound.

When operating in accordance with the present inven- 7 the compounds maybe applied to the fungus organisms sprayers and spray dusters.

able amount of any phytotoxic diluents.

Example 1 Twenty-five parts by weight ofbicyclohexyll-aminehydrochloride ot-isomer (melting at 295 "-300") ismixed and ground with 71 parts of fullers earth, 2 parts of an alkylaryl sulfonate (Nacconol NR), and 2 parts of a substituted benzoid alkylsulfonic acid (Daxad No. 27) to prepare a concentrate composition in theform of a wettable powder. In a similar manner, other amine concentratecompositions are prepared by employing one ofbicyclohexyl-4-amine-hydroiodide a-isoiner, mono (bicycloheXyl4-amine)-sulfate tat-isomer, bis (bicyclohexyllamine)-chromate a-isomer,bis (bicyclohexyll-aminey molybdate ,B-isomer, and mono(bicyclohexyl-4-amine)- phosphate tat-isomer in place of thebicyclohexyl-4-amine hydrochloride. 7

In a like manner, a wettable powder concentrate co position is preparedby mixing and grinding together 25 parts by weight ofbicyclohexyl-4-amine-hydrochloride fl-isomer (melting at 228-32 C.),16.5 parts of zinc sulfate, 2 parts of an alkyl aryl sulfonate (NacconolNR), 2 parts of Daxad 27 and 54.5 parts of fullers earth. Also, 90 partsby weight of mono(bicyclohexyl-4- 'amine)-chromate OL-lSCll'lGl (meltingat l27129 C.) and 10 parts by weight of a sorbitan monolauratepolyoxyethylene derivative (Tween are mixed together to prepare awater-dispersible concentrate composition. In a similar manner, otherwater dispersible concentrates may be prepared by employing one ofbicyclohexyl-4- amine fi-ison'ier, mono-('bicyclohexyl-4-amine)sulfateisomer, bicyclohexyl-4amine-nitrate B-isomer andbicyclehexyl-4-amine-hydroiodide ,B-isomer in place of the mono(bicyclohexylt-amine) -chrornat'e.

These concentrate compositions may be dispersed in water to provideaqueous compositions having very desirable wetting properties. Thelatter aqueous compositions are adapted to be employed to distribute thebicyclohexyl-4- amine salt compounds in fungicidal amounts.

Example 2 A water dispersible concentrate composition was prepared bymixing and grinding together in a ball mill 0.06 part by weight ofbicyclohexyl-4-amine hydrobromide aisomer (melting at 22923l C.), 0.06part of an alkyl aryl sulfonate (Nacconol NR) and 0.06 part of Daxad No.27 and 200 parts of water. A portion of this concentrate was dilutedwith water to form aqueous spray compositions containing A2 and pound ofthe salt compound per 100 gallons of ultimate composition.

The latter spray compositions were sprayed with an atomizing spraynozzle using air pressure at 20 pounds per square inch on young tomatoplants 3 to 5 inches high. The applications'were carried out so as togive thorough coverage of all surfaces of the leaves of the plantswithout appreciable run oif. Following the application, the spraycomposition was allowed to dry upon the leaf surfaces and the plantsthen inoculated by spraying with an aqueous suspension of viable sporesof Alternaria solani, the casual organism of tomato early blight.Untreated tomato plants were similarly inoculated to serve as checks.Immediately following the inoculation, all plants were placed in a moistchamber and maintained at 70 F. under saturated humidity conditions for24 hours. Thereafter, the plants were placed in a shaded greenhouse for48 hoursand then observed for leisons caused by the blight organism. Thedosages at which the amine salt was employed together with the resultsof the observation expressed as percent control of Alternaria solani areset forth in the following table.

Concentration of (Bicyclohexyl)-4-amine hydro- Percent Control bromidein Pounds For Gallons of Spray of Alternaria Composition solanz' At thetime of the observations, the check plants were found to be heavilycovered with lesions attributable to Alternaria solam'. 7

Example 3 A water dispersible liquid concentrate was prepared by mixingand grinding together in a ball mill 0.06 part by weight ofbicyclohexyll-amine-nitrate alpha isomer (melting at 235 C.) 0.06 partof Daxad No. 27, 0.06 part'of Nacconol NR and 200 parts of water. Aportion of this concentrate was dispersed in water to prepare aqueousspray compositions containing and A; pound of the nitrate compound per100 gallons of ultimate mixture. These compositions were employedexactly as de'scribed'in Example 2 for the control of tomato earlyblight on tomato plants. The results obtained in these operations areset forth in the following table.

At the time of the observations, the check plants were found to beheavily covered with lesions attributable to Alternaria solani.

Example 4 A water dispersible liquid concentrate was prepared by mixingand grinding together in a ball mill 0.06 by weight ofbis(bicyclohexyl-4-amine)-sulfate alpha isomer, 0.06 part of Daxad No.27, 0.06 part of Nacconol NR and 200 parts of water.

In a similar manner, other dispersible liquid concentrates were preparedfrom bicyclohexyl-4-amine and various inorganic salts ofbicyclohexyl-4-amine. Portions of these concentrate compositions weredispersed in water to prepare spray compositions containing 43 pound ofone of the amine toxicants per 100 gallons of ultimate mixture. Thesespray compositions were employed exactly as described in Example 2 forthe control of tomato early At the time of the observations, the checkplants were found to be heavily covered with lesions attributable toAlternaria solani.

Example A portion of water dispersible concentrate compositioncontaining 0.50 part by weight of bicyclohexyl-4- amine-hydrobromidea-isomer, 2 parts of Nacconol NR, 2 parts of Daxad No. 27 and 200 partsof water is dispersed in water to prepare an aqueous spray compositioncontaining one pound of the hydrobromide ingredient per 100 gallons ofultimate mixture. This composition is applied in an apple orchard to thetrunks and branches of dormant trees and to the ground floor beneath thetrees for the control of the over wintering spores of apple scab. Theapplication is carried out with conventional spraying equipment, thespraycomposition being applied to the trees in an amount suflicient toprovide for appreciable run off. Unsprayed check trees are maintained inthe orchard to provide for a continuous source of reinfestation. Sixweeks following bloom, the trees are examined and compared with theuntreated check trees to determine what control of apple scab had beenobtained. As a result of the observations there is found a commercialcontrol of apple scab with heavy infestation on the untreated checks.

Example 6 A Wettable powder concentrate was prepared by mixing andgrinding together 25 parts by weight ofbicyclohexyl-4-amine-hydrochloride alpha isomer, 54.5 parts of fullersearth, 16.5 parts of zinc sulfate, 2 parts of Nacconol NR and 2 parts ofDaxad No. 27. A portion of this concentrate Was dispersed in water toprepare an aqueous spray composition containing one pound of the aminehydrochloride compound per 100 gallons of ultimate mixture. This spraycomposition was applied as a summer spray in an orchard of bearingcherry trees. The application was made with a conventional spray rig andin such amount as to provide for appreciable runoff from the treatedleaf and woody surfaces of the trees. Unsprayed check trees weremaintained in the orchard to provide a continuous source ofreinfestation. Four months following the applications, the trees weresubjected to randomized sampling and individual leaves examined todetermine the percent control of cherry leaf spot. As a result of theobservations, there was found an 85 percent control of cherry leaf spoton the treated trees with heavy infestation in the untreated checks.

Example 7 A water dispersible concentrate composition was prepared bymixing and grinding together in a ball mill 0.24

' and 200 parts of water.

In a similar manner other dispersible concentrate compositions wereprepared from various inorganic salts of bicyclohexyl-4-amine. Portionsof these concentrate compositions were dispersed in water to prepareaqueous spray compositions containing /2 pound of one of the aminetoxicants per 100 gallons of ultimate mixture. These spray compositionswere sprayed with an atomizing spray nozzle using a pressure at 20pounds per square inch on stands of wheat in the early two leaf stage.The applications were carried out so as to give thorough coverage of allsurfaces of the plants. Twentyfour hours following the applications theplants were inoculated with an aqueous suspension of the spores ofPztccinia graminis tritici, the casual organism of wheat rust. Untreatedstands of wheat in the early two leaf stage were similarly inoculated toserve as checks. Im-,

I e results obtained in these operations are set forth in the followingtable:

At the time of observation, the check plants were heavily infested withwheat rust.

The bicyclohexyl-4-amine as employed in accordance with the presentinvention occurs in two isomeric forms known as the alpha and betaisomers. These two isomers may be prepared by known methods. In suchmethods, 4-cyclohexylcyclohexanol is dehydrogenated over a coppercatalyst at 300 C. .to form 4-cyclohexylcyclohexanone, and this productthereafter ammoniated to form a 4- cyclohexyl-cyclohexanone amine. Thelatter is thereafter hydrogenated over a nickel catalyst at 60 C. and 75pounds pressure per square inch to give a reaction mixture containingabout equal amountsof the alpha and beta isomers ofbicyclohexyl-4-arnine. The hydrogen chloride .salt of the beta isomer ofthe amine is soluble in chloro form while the hydrogen chloride salt ofthe alpha isomer of the amine is substantially insoluble in chloroform.Thus, the isomeric amines may beseparated in the form of their hydrogenchloride salts, and the salts thereafter converted to the free amine.The hydrogen chloride salts of the alpha and beta isomers of the aminemelt at 295 300 C. and 228232 C., respectively, While the alpha isomerof. the amine melts at 58-62 C. and the beta isomer of the amine meltsat 32 C.

The bicyclohexyl-4-amine salt compounds as employed in accordance. withthe present invention conveniently may be prepared by reactingbicyclohexyl-4-amine with an inorganic acid such as hydrochloric acid,hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, chromicacid, chloric acid, molyb'dic acid or phosphoric acid.

When carrying out the reaction between the bicyclehexyl-4-amine andacid, the salt compounds are produced in the form of the monoorpolyamine salts of the acids depending upon the basicity of the employedacid as well as upon the molecular proportions in which the amine andacid reactants are employed. Thus, for example, when a monoor polybasicacid is employed with an equimolecular amount of bicyclohexy1-4-amine,the mono-amine salt of the acid is produced. Similarly, when two orthree molecular proportions of bicyclohexyl- 4-amine are employed withone molecular proportion of a dibasic or tribasic acid, the bis(amine)salt of the dibasic acid, or the his amine salt of tris(amine) salt ofthe tribasic acid, respectively, are obtained. In carrying out thereaction, the bicyclohexyl-4-arnine is contacted portionwise with theinorganic acid in a reaction solvent such as water or ethanol and at atemperature of from 20 to C. Upon completion of the reaction, thereaction mixture may be cooled and filtered to separate the desired saltproduct.

I claim: p

l. A method which comprises applying to fungal organisms and theirhorticultural habitats a fungicidal amount of amine compound selectedfrom the group consisting of bicyclohexyl-4-amine and its inorganic acidsalts.

2. A method claimed in claim 1 wherein said amine 4. A method claimed inclaim 1 wherein said amine 7 compound is bicyclohexyl-4-aminehydrochloride a isomer.

5. A method claimed in claim 1 wherein said amin compound isbicyc1oheXyl-4amine hydrobromide aisomer.

6. A method claimed in claim 1 wherein said amine compound isbis(bicycloheXyl-4-amine)sulfate a-isomer.

7. A method claimed in claim 1 wherein said amine compound isbicyclohexylt-amine nitrate ot-isomer.

8. A fungicidal concentrate composition comprising an amine compoundselected from the group consisting of bicyclohexyll-amine and itsinorganic acid salts in intimate admixture with an inert fungicidaladjuvant 9. A fungicidal concentrate composition comprising an aminecompound selected from the group consisting of bicyclohexyl-4-amine andits inorganic acid salts as an active ingredient in intimate admixturewith from 1 to 20% by Weight of a surface-active dispersing agent.

10. A fungicidal concentrate composition comprising in an amount of atleast 0.001% by weight.

References Cited in the file of this patent UNITED STATES PATENTS I2,606,926 Kirby Aug. 12, 1952 2,606,928 Barkdoll Aug.'12, 1952 2,636,902Taylor Apr. 28, 1953 OTHER REFERENCES Horsfall: Fung. and Their Action,vol 11, Chronica Botanica Co., 1945, p. 131.

Frear: Chem. of Insect., Fung. and Herb., 2nd ed., 1948, D. Van NostrandCo., pp. 280-287.

1. A METHOD WHICH COMPRISES APPLYING TO FUNGAL ORGANISMS AND THEIRHORTICULTURAL HABITATS A FUNGICIDAL AMOUNT OF AMINE COMPOUND SELECTEDFROM THE GROUP CONSISTING OF BICYCLOHEXYL-4-AMINE AND ITS INORGANIC ACIDSALTS.